This invention relates to novel 2-alkyl-4-phenyl dihydropyrans and the use thereof in novel foodstuffs and foodstuff flavorings, chewing gums and toothpastes having green, floral, neroli-like, jasmine, peach-lactone-like aromas, and green vegetable-like flavors, processes for augmenting or enhancing neroli-like flavors and grape-like flavors, novel tobacco products, novel tobacco flavoring compositions, and processes for producing same, and has for an object the provision of a composition and process for improving the flavor and aroma of foodstuffs, chewing gums, toothpastes, tobacco and tobacco smoke.
It is well known in the tobacco art that the flavor and aroma of the tobacco product and the smoke from the tobacco are very important considerations insofar as the ultimate consumer is concerned. Considerable efforts have been and are being exerted by the manufacturers of tobacco products to provide a product that will be acceptable to the consumer, particularly as regards flavor and aroma characteristics. It has been the common practice in the tobacco industry to prepare blends of domestic and oriental tobaccos in order to provide smoking tobacco which has a pleasing flavor and aroma before and during smoking. However, such a procedure is costly and may at times become prohibitive in the event that certain types of tobacco may be in short supply. Accordingly, there has been considerable work relating to substances which can be used to impart flavors to various tobacco blends and to augment or enhance flavors of various tobacco blends. These substances are used to supplement natural materials some of which, as stated above, may be in short supply, and to provide more uniform properties to the finished product.
Sweet, spicy, coumarin-like and vanilla-like notes are particularly desirable for many uses concerning the flavoring of tobacco products; both prior to and on smoking.
Schumacher et al., U.S. Pat. No. 3,380,457, issued on Apr. 30, 1958 described an improved tobacco product containing a lactone compound having the generic structure: ##STR2## wherein one or more of R.sub.1, R.sub.2 and R.sub.3 are hydrogen or alkyl and wherein the dashed lines represents a single bond or a double bond. Schumacher et al. states that an aroma and flavor which is reminiscent of coconut may be imparted by the use of 3-isopropyl-delta-valerolactone as a tobacco additive; or by the use of 5-hydroxy-3-isopropyl-2-pentenoic acid delta lactone, as a tobacco additive; or a spicy note may be imparted by the use of 5-hydroxy-2-isopropylhexanoic acid delta lactone, as a tobacco additive; or a spicy apple note may be imparted by the use of beta-methyl-delta valerolactone as a tobacco additive.
There has been considerable work performed relating to substances which can be used to impart (or enhance) flavors to (or in) various foodstuffs, chewing gums and toothpastes. These substances are used to diminish natural materials, some of which may be in short supply, and to provide more uniform properties in the finished product. Green, floral, neroli-like, jasmine, peachlactone-like aromas, and green vegetable-like flavors are desirable for many uses in foodstuff flavors, chewing gum flavors and toothpaste flavors as well as the foodstuffs per se, the chewing gums per se and the toothpastes per se.
Dutch published application No. 6,808,496, published on December 19, 1969 (corresponding to British Pat. No. 1,281,813 published on July 19, 1972) discloses, for use in perfumery in order to provide fruity green scents with an overtone of floral muguet, compounds having the generic structure: ##STR3## Wherein A together with the carbon atoms C.sub.1, C.sub.2 and C.sub.3, forms a cyclic system which may either by monocyclic or polycyclic, e.g. bicyclic or tricyclic, and may carry one or more alkyl groups on the residue A; and R.sub.1 to R.sub.4 represents hydrogen atoms or alkyl groups having 1 to 5 carbon atoms with the exception that at least one of R.sub.1 to R.sub.4 represents an alkyl group when A represents a 1,2-ethylidene or 1,3-propylidene group. More specifically, structures 15, 16, 17, 18, 19, 20, 25 and 26 of the published Dutch Application No. 6,808,496 are as follows: ##STR4##
U.S. application for Letters Patent Ser. No. 547,057, filed on Feb. 4, 1975 and assigned to the Assignee of the instant application, International Flavors & Fragrances Inc., discloses methods for preparing foodstuffs, flavoring compositions for foodstuffs, perfume compositions, ingredients for perfume compositions, tobacco compositions and flavoring compositions for tobacco by including therein a pyran derivative (or mixtures thereof) of our invention having the structure: ##STR5## wherein R.sub.1 is hydrogen or methyl; wherein R.sub.2, R.sub.3, R.sub.4, R.sub.5 R.sub.6 and R.sub.7 represents hydrogen or C.sub.1 -C.sub.5 lower alkyl; wherein when one of R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6 or R.sub.7 is any of C.sub.2 -C.sub.5 lower alkyl, each of the other of the R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6 and R.sub.7 moieties is hydrogen; wherein each of the dashed lines represents a carbon-carbon single bond or a carbon-carbon double bond, with at least one of the dashed lines being a carbon-carbon single bond to produce:
(a) In food flavorings, dill, basil, valerian oil-like, caraway seed-like, thyme-like, piney, raspberry-like, blackberry-like, camphoraceous, herbaceous, eucalyptol-like, cooling, minty, ionone, tea-like, floral, sweet, fruity, woody, apple-like, petitgrain-like, smokey, leafy and green flavor notes. PA0 (b) In perfumes, green, floral, herbal, eucalyptol-like, sweet, minty and terpineol-like notes; and PA0 (c) In tobacco flavorings, aromatic, sweet, minty and cooling notes; PA0 ethyl; PA0 n-propyl; PA0 i-propyl; PA0 n-butyl; PA0 i-butyl; and PA0 t-butyl. PA0 Ethyl butyrate; PA0 Ethyl acetate; PA0 Ethyl valerate; PA0 Amyl acetate; PA0 Phenyl ethyl isovalerate; and PA0 Methyl heptynyl carbonate PA0 3-phenyl-2-pentenal; PA0 3-phenyl-3-pentenal; PA0 phenyl acetaldehyde; PA0 Cinnamaldehyde; and PA0 Beta-ethyl-cinnamaldehyde PA0 Benzylidene acetone; PA0 Acetophenone; PA0 Maltol; and PA0 Ethyl maltol PA0 3-phenyl-4-pentenal dimethyl acetal; and PA0 3-phenyl-4-pentenal diethyl acetal PA0 (described in copending application for U.S. Let. Pat. No. 276,922, filed on Aug. 1, 1972). PA0 Vanilla; PA0 Coffee extract; PA0 Origanum Oil; PA0 Cocoa Extract; PA0 Oil of Cloves; PA0 Nutmeg Oil; PA0 Celery seed oil; PA0 Bergamot oil; and PA0 Ylang-ylang oil PA0 Delta-decalactone; PA0 Delta-undecalactone; PA0 Delta-dodecalactone; PA0 Gamma-undecalactone; and PA0 Coumarin PA0 Dibenzyl ether; PA0 Vanillin; and PA0 Eugenol PA0 2-Acetyl pyrazine; PA0 2-Acetyl-6-methyl pyrazine; PA0 2-Ethyl pyrazine; PA0 2,3-Dimethyl pyrazine; PA0 2,5-Dimethyl pyrazine; and PA0 2-Ethyl-5-methyl pyrazine PA0 N-cyclopropyl pyrrole; and PA0 N-cyclooctyl pyrrole PA0 Natural orange oil; PA0 Methional; PA0 Rum ether; PA0 Diethyl malonate; PA0 Ethyl propionate; PA0 Amyl isovalerate; PA0 Acetic acid; PA0 Ethyl nonanoate; PA0 Phenyl ethyl acetate; PA0 Isobutyl formate; PA0 Methyl anthranilate; PA0 Ethyl heptanonate; PA0 Cinnamyl propionate; PA0 Ethyl acetate; PA0 Ethyl butyrate; PA0 Cinnamyl alcohol; PA0 Cinnamyl isovalerate; PA0 Cinnamyl propionate; PA0 Citral; PA0 Ethyl benzoate; PA0 Ethyl caproate; PA0 Ethyl methylphenylglycidate; PA0 Ethyl oenanthate; PA0 Ethyl pelargonate; PA0 Hydroxy citronellal; PA0 Petitgrain oil; PA0 Terpinenyl acetate; PA0 Tolualdehyde; PA0 Methyl naphthyl ketone; PA0 Benzylidene acetone, PA0 Alpha ionone, PA0 Lemon essential oil; and PA0 Lime essential oil.
foodstuff flavoring compositions, perfume compositions, perfumed articles, tobacco articles and tobacco compositions containing such pyran materials.
The compound 3,6-dihydro-2,4-dimethyl-6-phenyl-2H-pyran having the structure: ##STR6## as well as the compound 3,6-dihydro-2,4-dimethyl-6-phenyl-2H-pyran having the structure: ##STR7## are disclosed by Williams et al., Volume 72, J.Am.Chem.Soc. 5738-43 (1950) ["A Synthesis of Substituted Pyrans"] specifically at page 5741. However, the organoleptic properties of such compounds are not set forth.
The structures and organolpetic properties of compounds of the prior art are different in kind from the structures and organoleptic properties of the compounds of the instant invention.